
%0 Journal Article
%A Rizzardo, E 
%A Serelis, AK 
%A Solomon, DH 
%T Initiation mechanisms in radical polymerizations : Reaction of cumyloxy radicals with methyl methacrylate and styrene
%J Australian Journal of Chemistry
%D 1982/10/01
%V 35
%N 10
%P 2013-2024
%K 
%R https://doi.org/10.1071/CH9822013
%U https://www.publish.csiro.au/paper/CH9822013 
%X Cumyloxy (1-methyl-1-phenylethoxy) radicals have been generated by thermolysis (60º) of dicumyl hyponitrite in methyl methacrylate and styrene. The carbon-centred radicals formed by interaction of cumyloxyl with the respective monomers were trapped as stable adducts of 1,1,3,3-tetramethyl-isoindolin-2-yloxyl. Extensive hydrogen atom abstraction and methyl radical generation as well as double-bond addition were observed in methyl methacrylate. Styrene underwent only double-bond addition by both cumyloxy and methyl radicals. Some possible implications of these results for polymer structure are discussed. A kinetic study of the decomposition of dicumyl hyponitrite in cyclohexane at various temperatures gave  k=7.7 &#215; 1014exp(-13600/T) s-1 for the rate constant. Rate constants for the addition of cumyloxyl to methyl methacrylate (k &#8776; 2 &#215; 104 dm3 mol-1 s-1) and styrene (k&#8776;2 &#215; 105 dm3 mol-1 s-1) at 60ºhave been estimated. 
